Compositions and methods for filter cake removal

ABSTRACT

The present disclosure provides compositions for removing filter cake from a subterranean borehole and methods for degrading filter cake and filter cake removal. The composition contains an encapsulated peroxygen (e.g., acrylic resin coated ammonium persulfate), a surfactant (e.g., nonionic surfactant), and optionally an unencapsulated peroxygen. The method (e.g., a one-step method) involves contacting the filter cake with the composition, and allowing the composition to remain in contact with the filter cake for a period of time sufficient to degrade the filter cake. The reaction of the composition with the filter cake results in acidic conditions, thereby eliminating any need for follow up acid treatments. The composition is stable enough to effectively remove filter cake at temperatures up to 250° F. or greater. Through filter cake removal, the method provides for increased flow, production, and/or recovery of oil and gas hydrocarbons from a subterranean formation.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Ser.No. 62/175,817, filed on Jun. 15, 2015, and U.S. Provisional ApplicationSer. No. 62/232,984, filed on Sep. 25, 2015, and is a divisionalapplication of U.S. application Ser. No. 15/175,812, filed Jun. 7, 2016,all of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE DISCLOSURE 1. Field of the Disclosure

The present disclosure relates to a composition for removing filter cakefrom a subterranean borehole and a method for filter cake removal. Moreparticularly, the present disclosure relates to a composition for filtercake removal containing an encapsulated peroxygen (e.g., acrylic resincoated ammonium persulfate), a surfactant (e.g., nonionic surfactant),and optionally an unencapsulated peroxygen. The method (e.g., a one-stepprocess) involves contacting the filter cake with the composition, andallowing the composition to remain in contact with the filter cake for aperiod of time sufficient to degrade the filter cake. The compositionreaction with the filter cake results in acidic conditions, therebyeliminating any need for follow up acid treatments.

2. Description of the Related Art

Drilling muds are used in the oil and gas industry during the process ofdrilling boreholes into the earth. The addition of drilling muds (ordrilling fluids) has multiple functions, including providing hydrostaticpressure to prevent formation fluids from entering the wellbore,prevention of formation damage, keeping the drill bit cool, and liftingand suspending drill cuttings to the surface. Drilling muds can eitherbe water-based muds, or oil-based muds. Oil-based drilling fluids areused in formations with clays that react, swell, or slough when exposedto water-based fluids, and are also able to be used at highertemperatures.

As the drilling fluid is forced against permeable mediums within thewellbore, residue is deposited resulting in the formation of filtercake, or mudcake. Upon completion of the drilling, the mudcake must beremoved to allow production of the formation fluids. Removal of thefilter cake must be as complete as possible in order to recoverpermeability within the formation.

A common problem with current treatment methods is the lack of controlin uniform breakdown of the filter cake which results in worm holes,through which the treatment fluid then enters. As such, currenttreatment methods may include multiple treatment steps to achieve thedesired outcome, including an acid injection treatment to dissolvecarbonates, found in the mud, and/or certain polymers.

Several methods of filter cake removal exist which include beginningwith a filter cake composition designed to react with a subsequenttreatment step. Dobson, Jr. et al., U.S. Pat. No. 5,607,905 teaches aprocess for enhancing removal of filter cake wherein an alkaline earthmetal peroxide as an integral component is deposited within the filtercake. Upon contacting the filter cake with an acid solution treatment,the peroxide becomes activated for a period of time such that thepolymer within the filter cake will decompose. Hollenbeck et al. U.S.Pat. No. 4,809,783 teach a method for dissolvingpolysaccharide-containing filter cake by injecting effective amounts oftreatment fluid comprising a soluble source of fluoride ions present inan amount sufficient to provide a molar concentration of from about 0.01to about 0.5, having a pH in the range of from about 2 to about 4.Hollenbeck also teaches that the said treatment fluid may contain aneffective amount of oxidizer capable of degrading the polysaccharidepresent in the filter cake upon disruption of the metalion-polysaccharide complex. That oxidizer may be sodium persulfate.

Hossaini et al. U.S. Pat. No. 6,886,635 discloses a method of removingfilter cake from a subterranean borehole that involves drilling theborehole with a fluid that includes additives to form a filter cakehaving an oxidant-degrading component, preferably a polysaccharide. Thefilter cake is contacted with a brine solution containing persulfatesalt to degrade polymers within the filter cake, in well bores havingtemperatures ranging from about 65° F. to 165° F. The pace of thereaction is dependent on the concentration of persulfate. Hossaini etal. also teach this method further involves a step of flushing away thedecomposed filter cake with low concentration of acid. Data tablesdemonstrate the need for a follow up acid treatment in order to achieveeffective results of above 90% recovered production permeability, at alltemperatures tested.

Each of these methods includes dependency on a previous or subsequentstep in order to achieve the most effective results. A need exists for asingle treatment which will provide effective, controlled, uniformfilter cake breakdown under a wide temperature range. The singletreatment should be capable of achieving over 90% recoveredpermeability.

SUMMARY OF THE DISCLOSURE

The present disclosure provides a composition for removing filter cakefrom a subterranean borehole and a method for filter cake removal. Moreparticularly, the disclosure provides a composition for filter cakeremoval containing an encapsulated peroxygen (e.g., acrylic resin coatedammonium persulfate), a surfactant (e.g., nonionic surfactant), andoptionally an unencapsulated peroxygen.

The present disclosure provides a composition for removing filter cakefrom a subterranean borehole and a method for filter cake removal whichis effective at temperatures up to 250° F. or greater. Moreparticularly, the disclosure provides a composition containing anencapsulated peroxygen (e.g., acrylic resin coated ammonium persulfate),a surfactant (e.g., nonionic surfactant), and optionally anunencapsulated peroxygen which effectively removes filter cake attemperatures as high as 250° F. or greater.

The present disclosure provides a one-step method for degrading filtercake. The method involves contacting the filter cake with a compositioncomprising (a) an encapsulated peroxygen; (b) a surfactant; andoptionally (c) an unencapsulated peroxygen; and allowing the compositionto remain in contact with the filter cake for a period of timesufficient to degrade the filter cake. The reaction of the compositionwith the filter cake results in acidic conditions, thereby eliminatingany need for follow up acid treatments.

The present disclosure provides compositions and methods of using asingle fluid treatment for removing filter cake from a subterraneanborehole to increase flow, production, and/or recovery of oil and gas.The compositions include coated peroxygen compounds, surfactant, andoptionally uncoated peroxygen compounds, and the treatment methodcreates acidic conditions.

In accordance with this disclosure, a method is provided for removingfilter cake from subterranean boreholes and wellbores in a one-steptreatment process at temperatures up to 250° F. or greater. Thecomposition can include a surfactant with an encapsulated peroxygencompound and optionally an unencapsulated peroxygen compound. At leastone component can be mixed with fresh water, brine water, formationwater, water with potassium chloride or other salts added, orcombinations prior to introduction into the subterranean formation. Theencapsulation or coating provides a controlled release of peroxygendegradant, allowing more uniform breakdown of filter cake throughout thewellbore. The treatment may also comprise a cosolvent to aid indissolving oils and further breakdown of oil based filter cakes. Thereaction of this composition with the filter cake results in acidicconditions, thereby eliminating any need for follow up acid treatments.

The present disclosure provides method of removing filter cake from asubterranean borehole. The method comprises drilling a borehole with adrill-in fluid to form a filter cake; contacting the filter cake with acomposition comprising (a) an encapsulated peroxygen (e.g., acrylicresin coated ammonium persulfate); and (b) a surfactant; and allowingthe composition to remain downhole for a period of time sufficient todegrade the filter cake.

The present disclosure also provides a method of removing filter cakefrom a subterranean borehole. The method comprises drilling a boreholewith a drill-in fluid to form a filter cake; contacting the filter cakewith a composition comprising (a) an encapsulated peroxygen (e.g.,acrylic resin coated ammonium persulfate); (b) a surfactant; and (c) anunencapsulated peroxygen; and allowing the composition to remaindownhole for a period of time sufficient to degrade the filter cake.

The present disclosure further provides a method of removing filter cakefrom a subterranean borehole. The method comprises drilling a boreholewith a drill-in fluid to form a filter cake; contacting the filter cakewith a composition comprising (a) an unencapsulated peroxygen; and (b) asurfactant; and allowing the composition to remain downhole at atemperature from about 180° F. to about 250° F. and for a period of timesufficient to degrade the filter cake.

The present disclosure yet further provides a composition for removingfilter cake from a subterranean borehole. The composition comprises (a)an encapsulated peroxygen (e.g., acrylic resin coated ammoniumpersulfate); and (b) a surfactant.

The present disclosure also provides a composition for removing filtercake from a subterranean borehole. The composition comprises (a) anencapsulated peroxygen (e.g., acrylic resin coated ammonium persulfate);(b) a surfactant; and (c) an unencapsulated peroxygen.

The present disclosure further provides a composition for removingfilter cake from a subterranean borehole in which the filter cake ischemically broken down by the composition via direct oxidation or freeradical oxidation. The composition contains an oxidant that may be anencapsulated peroxygen and/or an unencapsulated peroxygen.

The present disclosure preferably provides a one step process forremoving filter cake from subterranean boreholes and wellbores. Thereaction of any of the compositions of this disclosure with the filtercake results in acidic conditions, thereby eliminating any need forfollow up acid treatments.

Through filter cake removal, the compositions and methods of thisdisclosure provide for increased flow, production, and/or recovery ofoil and gas hydrocarbons from a subterranean formation.

These and other systems, methods, objects, features, and advantages ofthe present disclosure will be apparent to those skilled in the art fromthe following detailed description of the preferred embodiment and thedrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a table showing ingredients and amounts thereof of anoptimized oil-based drilling mud prepared in Example 1.

FIG. 2 is a table showing properties of a core sample in Example 1.

FIG. 3 is a table showing conditions used in breaking the filter cake inExample 2.

FIG. 4 is a table and photographs showing filter cake removal results inExample 2.

FIG. 5 is a table showing filtrate analysis for Na⁺, K⁺, Mg²⁺, Ca²⁺,Fe^(2+/3+) and Al³⁺ in Example 2.

FIG. 6 is a table showing conditions used in breaking the filter cake inExample 3.

FIG. 7 is a table and photographs showing filter cake removal results inExample 3.

FIG. 8 is a table showing filtrate analysis for Na⁺, K⁺, Mg²⁺, Ca²⁺,Fe^(2+/3+) and Al³⁺ in Example 3.

FIG. 9 is a table showing conditions used in breaking the filter cake inExample 4.

FIG. 10 is a table and photographs showing filter cake removal resultsin Example 4.

FIG. 11 is a table showing filtrate analysis for Na⁺, K⁺, Mg²⁺, Ca²⁺,Fe^(2+/3+) and Al³⁺ in Example 4.

FIG. 12 is a table showing conditions used in breaking the filter cakein Example 5.

FIG. 13 is a table and photographs showing filter cake removal resultsin Example 5.

FIG. 14 is a table showing filtrate analysis for Na⁺, K⁺, Mg²⁺, Ca²⁺,Fe^(2+/3+) and Al³⁺ in Example 5.

FIG. 15 is a table showing filter cake removal efficiencies and final pHresults in Example 6.

DESCRIPTION OF THE EMBODIMENTS

Embodiments of the present disclosure are described more fullyhereinafter with reference to the accompanying drawings, in which some,but not all, embodiments of the present disclosure are shown. Indeed,the present disclosure can be embodied in many different forms andshould not be construed as limited to the embodiments set forth herein.Rather, these exemplary embodiments are provided so that the presentdisclosure satisfies applicable legal requirements. Also, like numbersrefer to like elements throughout.

In an embodiment, the present disclosure provides a composition forremoving filter cake from a subterranean borehole and a method forfilter cake removal. The filter cake removal allows for increasing flow,production, and/or recovery of oil and gas hydrocarbons from a wellboreor a portion of a subterranean formation. The composition can include anencapsulated peroxygen, a surfactant, and unencapsulated peroxygen, analkali metal chelate, and a cosolvent. For example, the encapsulatedperoxygen can be an encapsulated peroxide, an encapsulated source ofperoxide, encapsulated sodium persulfate, encapsulated potassiumpersulfate, encapsulated ammonium persulfate, and combinations thereof.For example, the surfactants can be nonionic plant based surfactantssuch as fatty alcohol ethoxylates, fatty acid ethoxylates, fatty acidesters, fatty acid methyl ester ethoxylates, alkyl polyglucosides,polyalcohol ethoxylates, soy alkyltrimethyl ammonium chlorides, orcombinations. For example, the unencapsulated peroxygen can be anunencapsulated hydrogen peroxide, an unencapsulated source of hydrogenperoxide, unencapsulated sodium persulfate, unencapsulated potassiumpersulfate, unencapsulated ammonium persulfate, and combinationsthereof. Examples of solvents include, for example, terpenoid- or methylsoyate-ethyl lactate-, methyl lactate- or ethyl acetate-based compoundsor combinations. Examples of alkali metal chelates are sodium orpotassium chelates. The alkali metal chelate can serve the purpose ofscavenging ionic or bound phases of metals in a formation, such as iron,thereby extending the life of the peroxygen and making the peroxygenmore stable in the well bore or subterranean formation and increasingthe peroxygen penetration in the formation. The surfactants andcosolvents can provide further stabilization of the peroxygens in thewell bore and subterranean formation. The stability of this compositionalso allows for treatment in formations with temperatures up to 250° F.or greater.

In another embodiment, the composition of this disclosure includes afluid for removing filter cake from a subterranean borehole therebyincreasing flow, production, and/or recovery of hydrocarbons from awellbore or a portion of a subterranean formation. The compositionincludes an encapsulated peroxygen, a surfactant, and optionally anunencapsulated peroxygen. The composition also optionally includes analkali chelate, e.g., a sodium or potassium chelate, and a cosolvent.The fluid is applied to a portion of a wellbore or an adjacentsubterranean formation, for example, as a drilling fluid, a well boretreatment, for oil or gas production stimulation, for slick waterfracturing, for enhanced oil recovery, and combinations of these.

The encapsulated peroxygen can be, for example, an encapsulatedperoxide, an encapsulated source of peroxide, encapsulated sodiumpersulfate, encapsulated potassium persulfate, encapsulated ammoniumpersulfate, and combinations thereof. The surfactant can be, forexample, a nonionic plant based surfactant such as fatty alcoholethoxylates, fatty acid ethoxylates, fatty acid esters, fatty acidmethyl ester ethoxylates, alkyl polyglucosides, polyalcohol ethoxylates,soy alkyltrimethyl ammonium chlorides, or combinations. The encapsulatedperoxygen compound can be present in a final concentration applied tothe wellbore or subterranean formation that varies from 0.01 to 20percent by weight of peroxygen, for example, from 0.01 to 10 percent byweight of peroxygen. The pH of the composition can be adjusted if neededto avoid pH changes in the formation.

In some embodiments, the concentration of the encapsulated peroxygenintroduced into the wellbore or subterranean formation is between about0.01 and about 20 percent by weight. The concentration is determined bydividing the weight of the encapsulated peroxygen by the total weight ofthe composition when it is introduced into the wellbore or subterraneanformation. In some embodiments, the concentration of encapsulatedperoxygen is greater than about 0.01, 0.05, or 0.1 percent by weight ofperoxygen. In some embodiments, the concentration of encapsulatedperoxygen is less than about 15, 12, 10, 8, or 5 percent by weight ofperoxygen. In some embodiments the concentration of encapsulatedperoxygen relative to the non-water components is greater than about 1,2, 5, or 10 percent by weight of peroxygen. In some embodiments theconcentration of encapsulated peroxygen relative to the non-watercomponents is less than about 35, 30 or 25 percent by weight ofperoxygen relative to the non-water components. The concentrationrelative to the non-water components is determined by dividing theweight of encapsulated peroxygen by the total weight of the non-watercomponents.

The encapsulating material is preferably derived from a polymericmaterial. Illustrative materials include, for example, acrylic resins,cross-linked hydrophilic polymers, polymethyl methacrylate, polystyrene,polyethylene glycol, polyurethane, and the like.

In accordance with this disclosure, the encapsulated peroxygen compoundscan be prepared by reacting a peroxygen compound and a polymericmaterial in an amount and under reaction conditions sufficient to formthe encapsulated peroxygen compounds.

The concentration of peroxygen compound and polymeric material can beany desired amount that is suitable for the particular application. Forthe purpose of producing encapsulated peroxygen compounds that aresuitable for use in removing filter cake, the amount of encapsulantmaterial (e.g., acrylic resin) is loaded based on the weighted mass ofperoxygen compound to be treated. The amount of polymeric material canrange from about 1% by weight to about 300% by weight or from about 5%by weight to about 75% by weight, or preferably from about 10% by weightto about 50% by weight, based on the total number of moles of peroxygencompound encapsulated, although it can also be outside of these ranges.

In accordance with this disclosure, the peroxygen chemically breaks downthe filter cake via a direct oxidation pathway or via a free radicalpathway.

The reaction conditions for preparing the encapsulated peroxygencompounds, such as temperature, pressure and contact time, can vary andany suitable combination of such conditions can be employed herein. Thereaction temperature can be between about 10° C. to about 100° C., andmore preferably between about 20° C. to about 80° C., and mostpreferably between about 30° C. to about 50° C. Normally, the reactionis conducted under ambient pressure and the contact time can vary from amatter of seconds or minutes to a few hours or greater. The reactantscan be added to the reaction mixture or combined in any order. Thecontact time employed may, for example, range from about 0.1 to about 24hours, preferably from about 0.5 to 15 hours, and more preferably fromabout 1 to 5 hours, although the contact time can be outside of theseranges.

The surfactant can be, for example, a nonionic surfactant selected froma fatty alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid ester,a fatty acid methyl ester ethoxylate, an alkyl polyglucoside, apolyalcohol ethoxylate, a soy alkyltrimethyl ammonium chloride, amonococoate, and combinations. The nonionic surfactant can be anethoxylated coco fatty acid, an ethoxylated coco fatty ester, anethoxylated cocoamide, an ethoxylated castor oil, a monococoate, andcombinations. The polyethylene glycol (PEG) coco fatty acids can have arange of 5 to 40 PEG groups. The Hydrophile-Lipophile Balance (HLB)range for the PEG coco fatty acid can be 10 to 19. The concentrationrange of this compound can be from 0.01 to 80 percent of the totalsurfactant in this composition. The ethoxylated plant oil-basedsurfactants consisting of a PEG castor oil can have a range of 2.5 to 40PEG groups. The Hydrophile-Lipophile Balance (HLB) range for the PEGcastor oil can be 2.1 to 16. The concentration range of this compoundcan be from 10 to 80 percent of the total surfactant in thiscomposition. The PEG cocamide can have a range of 2 to 20 PEG groups.The Hydrophile-Lipophile Balance (HLB) range for the PEG cocamide can be2 to 19. The concentration range of this compound can be from 10 to 80percent of the total surfactant in this composition. The sorbitan esterbased surfactants can have the following: sorbitan monooleate with anHLB of 4.8: sorbitan monolaurate with an HLB of 8.6; sorbitanmonopalmitate with an HLB of 6.5; and sorbitan monostearate with an HLBof 4.7. The ethoxylated sorbitan ester based surfactants can have thefollowing: polyoxyethylene (20) sorbitan monooleate with an HLB of 15;polyoxyethylene(20) sorbitan monopalmitate with an HLB of 15.6;polyoxyethylene(20) sorbitan monostearate with an HLB of 14.9; andpolyoxyethylene(20) sorbitan monooleate with an HLB of 15.0. Thesurfactant can be present in a final concentration as applied to thewellbore or subterranean formation that varies from 0.01 to 50 percent,for example, from 0.05 to 5 percent by weight.

In an embodiment, the surfactant can be, for example, a nonionicsurfactant selected from a fatty alcohol ethoxylate, a fatty acidethoxylate, a fatty acid ester, a fatty acid methyl ester ethoxylate, analkyl polyglucoside, a polyalcohol ethoxylate, a soy alkyltrimethylammonium chloride, a monococoate, and combinations thereof.

In another embodiment, the surfactant can be, for example, a nonionicsurfactant selected from an ethoxylated coco fatty acid, an ethoxylatedcoco fatty ester, an ethoxylated cocoamide, an ethoxylated castor oil, amonococoate, and combinations thereof.

In a further embodiment, the surfactant can be, for example, theethoxylated coco fatty acid can be a polyethylene glycol (PEG) cocofatty acid having a range of about 5 to about 40 PEG groups, and aHydrophile-Lipophile Balance (HLB) range from about 10 to about 19; theethoxylated castor oil can be a polyethylene glycol (PEG) castor oilhaving a range of about 2.5 to about 40 PEG groups, and aHydrophile-Lipophile Balance (HLB) range from about 2.1 to about 16; theethoxylated cocoamide can be a polyethylene glycol (PEG) cocamide havinga range of about 2 to about 20 PEG groups, and a Hydrophile-LipophileBalance (HLB) range from about 2 to about 19.

In a yet further embodiment, the surfactant can be, for example, thesurfactant can be a sorbitan ester selected from sorbitan monooleatehaving a Hydrophile-Lipophile Balance (HLB) range from about 2.8 toabout 8.8; sorbitan monolaurate having a Hydrophile-Lipophile Balance(HLB) range from about 4.6 to about 12.6; sorbitan monopalmitate havinga Hydrophile-Lipophile Balance (HLB) range from about 2.5 to about 10.5;and sorbitan monostearate having a Hydrophile-Lipophile Balance (HLB)range from about 2.7 to about 8.7.

In another embodiment, the surfactant can be, for example, thesurfactant can be an ethoxylated sorbitan ester selected from apolyethylene glycol (PEG) sorbitan monooleate having a range of about 2to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB)range from about 10 to about 20; a polyethylene glycol (PEG) sorbitanmonolaurate having a range of about 2 to about 40 PEG groups, and havinga Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; apolyethylene glycol (PEG) sorbitan monopalmitate having a range of about2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance(HLB) range from about 10 to about 20; and a polyethylene glycol (PEG)sorbitan monostearate having a range of about 2 to about 40 PEG groups,and having a Hydrophile-Lipophile Balance (HLB) range from about 10 toabout 20.

In some embodiments, the surfactant concentration in the compositionwhen introduced into the wellbore or subterranean formation may bebetween about 0.01 and about 50 percent by weight. The concentration ismeasured by dividing the weight of the total surfactant by the totalweight of the composition. The concentration may be greater than about0.01, 0.03, 0.05, 0.1, 0.5, or 1 by weight or less than about 50, 45,40, 35, 30, 25, 20, 15, 10, or 5 percent by weight. Relative to thenon-water components, the surfactant concentration may be greater thanabout 5, 10, 15, 20, 25, or 30 percent or less than about 95%, 90%, 85%,80%. The concentration relative to the non-water components isdetermined by dividing the weight of surfactant by the total weight ofthe non-water components in the composition.

The composition of this disclosure may optionally include anunencapsulated peroxygen such as, for example, an unencapsulatedperoxide, an unencapsulated source of peroxide, unencapsulated sodiumpersulfate, unencapsulated potassium persulfate, unencapsulated ammoniumpersulfate, and combinations thereof. The unencapsulated peroxygencompound can be present in a final concentration applied to the wellboreor subterranean formation that varies from 0.01 to 20 percent, forexample, from 0.01 to 10 percent by weight.

In some embodiments, the concentration of the unencapsulated peroxygenintroduced into the wellbore or subterranean formation is between about0.01 and about 20 percent by weight. The concentration is determined bydividing the weight of the unencapsulated peroxygen by the total weightof the composition when it is introduced into the wellbore orsubterranean formation. In some embodiments, the concentration ofunencapsulated peroxygen is greater than about 0.01, 0.05, or 0.1percent by weight. In some embodiments, the concentration ofunencapsulated peroxygen is less than about 15, 12, 10, 8, or 5 percentby weight. In some embodiments the concentration of unencapsulatedperoxygen relative to the non-water components is greater than about 1,2, 5, or 10 percent by weight. In some embodiments the concentration ofunencapsulated peroxygen relative to the non-water components is lessthan about 35, 30 or 25 percent by weight relative to the non-watercomponents. The concentration relative to the non-water components isdetermined by dividing the weight of unencapsulated peroxygen by thetotal weight of the non-water components.

The composition of this disclosure may optionally include a chelate,such as a mono-, di-, tri-, or tetra-sodium ethylenediaminetetraaceticacid (EDTA), a mono-, di-, tri-, or tetra-potassiumethylenediaminetetraacetic acid (EDTA) or sodiumethylenediamine-N,N-disuccinic acid (EDDS), or combinations. Theselected chelate can be present in a final concentration as applied tothe wellbore or subterranean formation that varies from 0.0001 to 5.0percent by weight. For example, the chelate can be sodium EDTA.

In some embodiments, the chelate concentration in the composition whenintroduced into the wellbore or subterranean formation may be betweenabout 0.00001 to 5.0 percent by weight. The concentration is determinedby dividing the weight of the chelate by the total weight of thecomposition. The concentration may be greater than about 0.0001,0.00002, 0.0001, 0.001, 0.002, 0.01, or 0.1 percent. The concentrationmay be less than about 5.0, 4.0, 3.0, 2.0, 1.0, or 0.5 percent. Thechelate concentration, relative to the non-water components may bebetween about 0.2 and about 5 percent by weight. The concentrationrelative to the non-water components is determined by dividing theweight of the chelate by the total weight of the non-water components ofthe composition. The concentration, relative to the non-watercomponents, may be greater than about 0.2, 0.5, 0.7, or 1.0 percent, orless than about 5, 4.5, 4, 3.5, 3, 2.5, or 2 percent by weight.

The composition of this disclosure may optionally include a cosolvent,such as a terpene, for example, hemiterpene, a monoterpene, asesquiterpene, a diterpene, a sesterterpene, a triterpene, atetraterpene, and combinations. For example, the terpene can be amonoterpene, such as geraniol; d-limonene, or terpineol, orcombinations. For example, the terpene can be a citrus derived terpene,or a terpene derived from conifers. The selected terpene concentrationin the composition can be present in a final concentration as applied tothe wellbore or subterranean formation that varies from 0.001% to 50% byweight, for example, from 0.01% to 10% by weight. A soy derivedcosolvent, such as methyl soyate, can be a cosolvent in the composition.The methyl soyate concentration can be present in a final concentrationas applied to the wellbore or subterranean formation that varies from0.001% to 50% by weight, for example, from 0.01% to 10% by weight. Ethyllactate, methyl lactate or ethyl acetate may also be used as cosolvents.

In some embodiments, the cosolvent concentration in the composition whenintroduced into the wellbore or subterranean formation may be betweenabout 0.001 and about 50 percent. The concentration is determined bydividing the weight of cosolvent by the total weight of the compositionintroduced into the wellbore or subterranean formation. In someembodiments, the concentration of cosolvent is greater than about 0.001,0.002, 0.005, 0.007, or 0.01 percent. In some embodiments, the cosolventconcentration is less than about 50, 30, 25, 20, 15, 10, 8, or 5percent. The cosolvent concentration, relative to the non-watercomponents may be between about 1 and about 40 percent by weight. Theconcentration, relative to the non-water components, is determined bydividing the weight of cosolvent by the total weight of the non-watercomponents in the composition. The concentration, relative to thenon-water components may be greater than about 1, 5, 7, 10, 12, or 15 byweight. The concentration, relative to the non-water components may beless than about 80, 75, 70, 65, 60, 55, 50, 45, or 40 percent by weight.

In some embodiments, the composition further comprises an antioxidant.The antioxidant may be, for example, a plant-derived polyphenol. Theplant-derived polyphenol may be, for example, derived from sorghum bran.An antioxidant can be included in the composition to stabilize andcontrol the rate of peroxygen decay.

In the method of this disclosure, filter cake formed on the walls of asubterranean borehole is removed by contacting the filter cake with acomposition containing an encapsulated peroxygen, a surfactant, andoptionally an unencapsulated peroxygen. Filter cakes are coatings thatreduce the permeability of formation walls. Formed during the drillingstage to limit losses from the well bore and protect the formation frompossible damage by fluids and solids within the well bore, filter cakelayers must be removed from the hydrocarbon-bearing formation so thatthe formation wall is restored to its natural permeability to allow forhydrocarbon production or cementing.

Filter cakes are typically formed with polymers that encapsulateparticles or solids which form a bridge over the formation pores.Drill-in fluids, including any bridging agents and polymers containedwithin the drilling fluid are well known in the art. In one preferredmethod of this disclosure, removing filter cake from a subterraneanborehole involves drilling the borehole with a drill-in fluid comprisinga polymer to form a filter cake. Preferably, the borehole is drilledwhile circulating a mud therein which comprises a polymer. The polymeris selected from a water soluble organic polymer, a water dispersibleorganic polymer, a water soluble bio-polymer, a water dispersiblebio-polymer and combinations thereof. For example, the polymer selectedcan be a cationic starch, an anionic starch or a nonionic starch.Optionally, the drill-in fluid comprises finely divided solids dispersedtherein to form a filter cake on surfaces of the borehole. Otheradditives can be used for stabilizing and viscosifying.

When the bore hole is ready for production, the filter cake must beremoved to allow for permeability of the formation walls. To remove thefilter cake, the filter cake is contacted with a mixture containing anencapsulated peroxygen, a surfactant, and optionally an unencapsulatedperoxygen in a variable density brine. In one aspect, the mixture canfurther include a chelating agent. Preferably, the coated peroxygen iscoated ammonium persulfate. Alternatively, the peroxygen is selectedfrom an alkali metal peroxygen, an alkaline earth metal peroxygen andcombinations thereof. The alkali metal peroxygen can be selected frompotassium persulfate, sodium persulfate, lithium persulfate andcombinations thereof, and the alkaline earth metal peroxygen can beselected from calcium persulfate, magnesium persulfate, and combinationsthereof. In one aspect, the effective concentration of peroxygen rangesfrom about 1 lb/bbl to about 50 lbs/bbl, preferably from about 4 lb/bblto about 48 lbs/bbl.

Filter cake break or removal time can be controlled by the concentrationof the coated peroxygen within the brine and also varies with downholetemperature. Increasing the concentration or at higher downholetemperatures results in increased filter cake break or removal.

The variable density brine can be selected from NH₄ Cl, NaCl, KCl,CaCl₂, ZnCl₂, and combinations thereof and, with these chloride brines,can have a density varying within a range of from about 8.3 lbs/gal. toabout 12.8 lbs/gal, preferably within a range of from about 8.5 lbs/gal.to about 10.4 lbs/gal.

Downhole temperatures differ according to the depth and location of theformation. The filter cake removal composition of this disclosure can beused at a wide range of downhole temperatures. In one preferred method,the mixture is allowed to remain at the downhole temperatures rangingfrom 65° F. to 165° F., or from 165° F. to 180° F., or from 180° F. to250° F., or greater than 250° F., for a period of time effective todegrade the filter cake, ranging from about 3.5 to about 48 hours ormore, depending on the state of well operations at the time. Morepreferably, the temperature ranges from about 70° F. to 165° F. and theperiod of time the mixture remains in contact with the filter cake is atleast 4 hours. In another preferred method, the mixture is allowed toremain at the downhole temperatures ranging from 165° F. to 250° F. andthe period of time the mixture remains in contact with the filter cakeis at least 4 hours.

The decomposed filter cake can then be flushed away with the acidicfiltrate formed by the method of this disclosure. An organic orinorganic acid is commonly known in the art to increase permeability.The reaction of the composition of this disclosure with the filter cakeresults in acidic conditions, thereby eliminating any need for follow upacid treatments required by conventional processes. The filtrate will beacidic, for example, with a pH from about 0.1 to about 4, preferablyfrom about 0.1 to about 2.5, and more preferably from about 0.1 to about1, depending on the period of time that the mixture remains in contactwith the filter cake.

In an alternative embodiment of this disclosure, the method of removingfilter cake from a subterranean borehole involves contacting the filtercake with a mixture of an encapsulated peroxygen, a surfactant, andoptionally an unencapsulated peroxygen in a variable density bromide orchloride brine. The brine can be selected from NH₄ Cl, NH₄ Br, NaCl,NaBr, KCl, KBr, CaCl₂, CaBr₂, ZnCl₂, ZnBr₂, and combinations thereof. Inthis preferred method, the mixture is allowed to remain at the downholetemperatures for a period of time effective to degrade the filter cake.The peroxygen is selected from ammonium persulfate, an alkali metalpersulfate, an alkaline earth metal persulfate and combinations thereof.The density can vary within a range of from about 8.3 lbs/gal. to ashigh as about 18 lbs/gal. if a bromide brine is used.

A preferred composition for a filter cake removal fluid can comprise asolution of an encapsulated peroxygen, a surfactant, and optionally anunencapsulated peroxygen in a brine, the concentration of coatedperoxygen effective for filter cake break or removal at temperaturesbetween 65° F. to 180° F., preferably, between 65° F. to 165° F., orbetween 165° F. to 180° F., or between 180° F. and 250° F., or greaterthan 250° F. Preferably concentration of coated peroxygen ranges fromabout 1 lb/bbl to about 50 lbs/bbl, preferably from about 4 lbs/bbl toabout 48 lbs/bbl, and more preferably, the concentration ranges from 16lbs/bbl to 48 lbs/bbl. The solution of an encapsulated peroxygen, asurfactant, and optionally an unencapsulated peroxygen in a brine canhave a density within a range of about 8.3 lbs/gal to about 12.8lbs/gal. The coated peroxygen is preferably selected from coatedammonium persulfate, a coated alkali metal persulfate, a coated alkalineearth metal persulfate, and combinations thereof.

Illustrative steps for implementing the method of this disclosureinclude, for example, installing gravel pack screens and tool assembliesinto the borehole. Thereafter introducing sand in a non-viscosifiedcarrier into the borehole; and introducing a filter cake removal fluidof this disclosure in the well bore, in contact with a subterraneanformation containing the hydrocarbons to be produced, for a durationeffective to substantially remove the filter cake in the vicinity of thesubterranean formation. The filter cake removal fluid preferablycomprises a solution of an encapsulated peroxygen, a surfactant, andoptionally an unencapsulated peroxygen in a brine having a densitywithin a range of about 8.3 lbs/gal to about 12.8 lbs/gal, and themixture of coated peroxygen, surfactant, and optionally uncoatedperoxygen is effective for filter cake break or removal at temperaturesbetween 65° F. to 165° F., or between 180° F. and 250° F., or greaterthan 250° F.

Fluid loss pills can be used to form the filter cake. In an alternativemethod of removing filter cake from an existing subterranean borehole inwhich a fluid loss pill is used, the method comprises placing a fluidloss pill into the borehole, the fluid loss pill having a polymer toform a filter cake. In this method the polymer is selected from a watersoluble organic polymer, a water dispersible organic polymer, a watersoluble bio-polymer, a water dispersible bio-polymer and combinationsthereof. The filter cake is contacted with a mixture of an encapsulatedperoxygen, a surfactant, and optionally an unencapsulated peroxygen in avariable density brine. The peroxygen is preferably selected fromammonium persulfate, alkali metal persulfate, alkaline earth metalpersulfate and combinations thereof, and the brine can be selected formNH₄ Cl, NaCl, KCl, CaCl₂, ZnCl₂, and combinations thereof. In thismethod the mixture is allowed to remain at the downhole temperaturesranging from 65° F. to 165° F., or from 180° F. to 250° F., or greaterthan 250° F., for a period of time effective to degrade the polymerfilter cake. Alternatively the brine is selected from NH₄ Cl, NH₄ Br,NaCl, NaBr, KCl, KBr, CaCl₂, CaBr₂, ZnCl₂, ZnBr₂ and combinationsthereof and allowing the mixture to remain at the downhole temperaturesranging from 65° F. to 165° F., or from 180° F. to 250° F., or greaterthan 250° F., for a period of time effective to degrade the polymerfilter cake.

High permeability, soft sandstone formations, often found in horizontaldrilling, generally require some form of barrier for hole stability.Gravel packing is used to improve hole stability in these conditions.During the practice of this disclosure one method of removing filtercake from a subterranean borehole, comprises drilling the borehole whilecirculating a mud therein which comprises a polymer, the polymer isselected from a water soluble organic polymer, a water dispersibleorganic polymer, a water soluble bio-polymer, a water dispersiblebio-polymer and combinations thereof.

Following the drilling of a well, when fluid losses are acceptable forthe proposed pumping pressures, gravel or sand packing can begin. Firstthe drill-in fluid is displaced with a first clear fluid, which isotherwise similar to the drilling fluid. The well bore is maintained ina slightly overbalanced state. Gravel pack screens and tool assembliesare run into the bore. During this stage, it is desirable to maintainthe filter cake with as little fluid loss to the production formation aspossible. Following displacement of the drilling fluid, the well isgravel packed. In a preferred procedure, the gravel, preferably sizedsand, about 20-30 U.S. mesh, is placed into a nonviscosified carrier,such as a brine. Advantageously, the method of this disclosure comprisesthe simultaneous application of coated peroxygen, surfactant, andoptionally uncoated peroxygen with the gravel pack. Alternatively, atthe same time, or at a later time, coated peroxygen, surfactant, andoptionally uncoated peroxygen can be added to the gravel pack.Alternatively, coated peroxygen, surfactant, and optionally uncoatedperoxygen can be added independently of the gravel pack and also used insystems that do not employ gravel packing.

As the low viscosity fluid cannot transport a significant amount ofsolids, the sand concentrations are usually from about 60 g/l to 360 g/land pump rates approach 1 m³/min. The hydrostatic overbalance thatarises from the pumping pressure necessary to achieve these rates isdesirable since the overbalance holds the filter cake in place. A filtercake removal fluid is then introduced in the wellbore, in contact with asubterranean formation containing the hydrocarbons to be produced, for aduration effective to substantially remove the filter cake in thevicinity of the subterranean formation. Preferably, the filter cakeremoval fluid comprises a solution of an encapsulated peroxygen, asurfactant, and optionally an unencapsulated peroxygen in a brine havinga density within a range of about 8.3 lbs/gal to about 12.8 lbs/gal andeffective for degradation at temperatures between 65° F. to 165° F., orbetween 180° F. to 250° F., or greater than 250° F. The non-viscosifiedcarrier for the sand can comprise the filter cake removal fluid.

In the practice of this disclosure, other additives, such as claytreating additives, pH control agents, lubricants, non-emulsifyingagents, iron control agents and the like can be included within thefilter cake removal fluid or gravel pack fluid as desired.

In an embodiment, the method of the present invention includes applyinga liquid treatment fluid to a portion of a wellbore or a portion of asubterranean formation with a composition including an encapsulatedperoxygen (e.g., acrylic resin coated ammonium persulfate), asurfactant, optionally an unencapsulated peroxygen, optionally an alkalichelate (e.g., a sodium or potassium chelate), and optionally acosolvent. The method can include the following: forming or providingthe composition; and introducing the composition through a wellbore toapply it to a portion of a wellbore or a portion of a subterraneanformation. The liquid treatment fluid can be applied to a portion of awellbore or subterranean formation by pumping, displacing, or otherwiselocating the fluid to a desired location within the wellbore orsubterranean formation for treatment, at a rate and pressure that isless than, equal to, or greater than the reservoir hydraulic fracturepressure. The liquid treatment fluid can be applied to a portion ofwellbore or subterranean formation as a drilling fluid, as a chemicaltreatment, in an oil, gas, or water flow stimulation method, forhydraulic fracturing, in an enhanced oil recovery technique, andcombinations. The liquid treatment fluid can be applied to asubterranean formation or a hydrocarbon-bearing subterranean formationthat is geologically characterized as unconsolidated or consolidated andwhere the geologic material is, for example, sand, rock, clay, shale,carbonate, dolomite, coal, an argillaceous mineral, a mineral, or ahydrocarbon-containing geologic material, and combinations. For example,the temperature of the geological formation that can be treated usingthe disclosed composition and methods of this invention can range from50° F. to 250° F., or greater than 250° F.

As part of the methods for application, the composition of thisdisclosure can be allowed to contact the wellbore or a portion of a wellbore or subterranean formation or hydrocarbon-bearing subterraneanformation for a sufficient period of time to degrade filter cake, andincrease flow, production, and/or recovery of hydrocarbons. Thecomposition can be allowed to contact a portion of the well bore, thesubterranean formation, a lenticular lens or other types of lens withina formation, the formation cap, the formation base, or a formationinterface for a sufficient time, so that the permeability, relativepermeability, and/or absolute permeability are increased, causing anincrease in the flow, production, and/or recovery of hydrocarbons fromthe well bore. Adequate time can be allowed for contact of the disclosedcomposition. Such a sufficient or adequate time can be, for example,from about 1 minute, 2 minutes, 5 minutes, 15 minutes, 30 minutes, 1hour, 2 hours, 6 hours, 12 hours, 1 day, 2 days, 4 days, 1 week, 2weeks, 1 month, 2 months, 3 months, or 6 months to about 2 minutes, 5minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 6 hours, 12 hours, 1day, 2 days, 4 days, 1 week, 2 weeks, 1 month, 2 months, 3 months, 6months, or 12 months.

Sufficient time can be allowed for the composition to degrade the filtercake. The treatment can cause such targeted areas of a subterraneanformation to have an increased permeability, relative permeability,and/or absolute permeability. The composition can be applied withsufficient time allowed for the composition to degrade the filter cakewith sufficient action to physically alter, fragment, fracture, crack,pit, and/or create fluid preferential pathways within a portion of thetreated subterranean formation, wherein the permeability, relativepermeability, and/or absolute permeability is increased. The compositioncan be applied with sufficient time allowed for the composition todegrade the filter cake with sufficient action to mobilize, release,migrate, realign, and/or redistribute portions of the treatedsubterranean formation, clays, fines (inorganic and/or organic), sand,precipitates, minerals, and/or individual grains of the treatedsubterranean formation. These mobilized, released, or otherwise movedcomponents can be removed from the formation and carried into thewellbore along with produced fluids.

Preferred embodiments of this disclosure are described below.

A method of removing filter cake from a subterranean borehole, themethod comprising: drilling a borehole with a drill-in fluid to form afilter cake; contacting the filter cake with a composition comprising(a) an encapsulated peroxygen; and (b) a surfactant; and allowing thecomposition to remain downhole for a period of time sufficient todegrade the filter cake.

The method of paragraph [0081], wherein the peroxygen chemically breaksdown the filter cake via a direct oxidation pathway or via a freeradical pathway.

The method of paragraph [0081], further comprising removing the degradedfilter cake from the subterranean borehole.

The method of paragraph [0081], wherein the treatment generates acidicconditions.

The method of paragraph [0081], wherein the composition furthercomprises a variable density brine.

The method of paragraph [0081], wherein at least one component of thecomposition is mixed with fresh water, brine water, formation water withpotassium chloride or other salts added, or combinations thereof, priorto introduction into the subterranean borehole.

The method of paragraph [0081] wherein the encapsulated peroxygen isselected from the group consisting of encapsulated hydrogen peroxide, anencapsulated source of hydrogen peroxide, encapsulated sodiumpersulfate, encapsulated potassium persulfate, encapsulated ammoniumpersulfate, and combinations thereof.

The method of paragraph [0081], wherein the encapsulated peroxygen isselected from the group consisting of encapsulated hydrogen peroxide, anencapsulated source of hydrogen peroxide, encapsulated sodiumpersulfate, encapsulated potassium persulfate, encapsulated ammoniumpersulfate, and combinations thereof.

The method of paragraph [0081], wherein the encapsulated peroxygen iscured acrylic resin encapsulated peroxygen.

The method of paragraph [0081], wherein the encapsulated peroxygen iscoated ammonium persulfate.

The method of paragraph [0081], wherein the encapsulated peroxygenprovides a controlled time release of the peroxygen.

The method of paragraph [0081], wherein the peroxygen from theencapsulated peroxygen decomposes from a direct reduction reaction, asurface catalyzed reaction, and/or a free radical decompositionreaction.

The method of paragraph [0081], wherein the surfactant is nonionic.

The method of paragraph [0081], wherein the surfactant is selected fromthe group consisting of an ethoxylated plant oil based surfactant, afatty alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid amideethoxylate, a fatty acid ester, a fatty acid methyl ester ethoxylate, analkyl polyglucoside, a polyalcohol ethoxylate, a sorbitan ester, a soyalkyltrimethyl ammonium chloride, an ethoxylated coco fatty acid, anethoxylated coco fatty ester, an ethoxylated cocoamide, an ethoxylatedcastor oil, and combinations thereof.

The method of paragraph [0081], wherein the surfactant comprises anonionic surfactant selected from the group consisting of a fattyalcohol ethoxylate, a fatty acid ethoxylate, a fatty acid ester, a fattyacid methyl ester ethoxylate, an alkyl polyglucoside, a polyalcoholethoxylate, a soy alkyltrimethyl ammonium chloride, a monococoate, andcombinations thereof.

The method of paragraph [0081], wherein the surfactant comprises anonionic surfactant selected from the group consisting of an ethoxylatedcoco fatty acid, an ethoxylated coco fatty ester, an ethoxylatedcocoamide, an ethoxylated castor oil, a monococoate, and combinationsthereof.

The method of paragraph [0096], wherein the ethoxylated coco fatty acidis a polyethylene glycol (PEG) coco fatty acid having a range of about 5to about 40 PEG groups, and a Hydrophile-Lipophile Balance (HLB) rangefrom about 10 to about 19; the ethoxylated castor oil is a polyethyleneglycol (PEG) castor oil having a range of about 2.5 to about 40 PEGgroups, and a Hydrophile-Lipophile Balance (HLB) range from about 2.1 toabout 16; the ethoxylated cocoamide is a polyethylene glycol (PEG)cocamide having a range of about 2 to about 20 PEG groups, and aHydrophile-Lipophile Balance (HLB) range from about 2 to about 19.

The method of paragraph [0081], wherein the surfactant comprises asorbitan ester selected from the group consisting of sorbitan monooleatehaving a Hydrophile-Lipophile Balance (HLB) range from about 2.8 toabout 8.8; sorbitan monolaurate having a Hydrophile-Lipophile Balance(HLB) range from about 4.6 to about 12.6; sorbitan monopalmitate havinga Hydrophile-Lipophile Balance (HLB) range from about 2.5 to about 10.5;and sorbitan monostearate having a Hydrophile-Lipophile Balance (HLB)range from about 2.7 to about 8.7.

The method of paragraph [0081], wherein the surfactant comprises anethoxylated sorbitan ester selected from the group consisting of apolyethylene glycol (PEG) sorbitan monooleate having a range of about 2to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB)range from about 10 to about 20; a polyethylene glycol (PEG) sorbitanmonolaurate having a range of about 2 to about 40 PEG groups, and havinga Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; apolyethylene glycol (PEG) sorbitan monopalmitate having a range of about2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance(HLB) range from about 10 to about 20; and a polyethylene glycol (PEG)sorbitan monostearate having a range of about 2 to about 40 PEG groups,and having a Hydrophile-Lipophile Balance (HLB) range from about 10 toabout 20.

The method of paragraph [0081], wherein the surfactant is present in thecomposition, when the composition is introduced into the wellbore orsubterranean formation, in an amount from about 0.01 to about 50 percentby weight, based on the total weight of the composition.

The method of paragraph [0081], further comprising a chelate, whereinthe chelate is selected from the group consisting of a mono-, di-, tri-or tetra-sodium ethylenediaminetetraacetic acid (EDTA), a mono-, di-,tri- or tetra-potassium ethylenediaminetetraacetic acid (EDTA), sodiumethylenediamine-N,N′-disuccinic acid (EDDS), and combinations thereof.

The method of paragraph [0081], further comprising a cosolvent, whereinthe cosolvent is selected from the group consisting of a terpene, methylsoyate, ethyl lactate, methyl lactate, ethyl acetate, and combinationsthereof.

The method of paragraph [0081], wherein the encapsulated peroxygen andsurfactant are added simultaneously or sequentially to the composition.

The method of paragraph [0081], wherein the composition is applied tothe subterranean borehole as, or in combination with, a drilling fluid,treatment fluid, stimulation fluid, fracturing fluid, a fluid used in anenhanced oil recovery technique, or a combination thereof.

The method of paragraph [0081], further comprising: allowing thecomponents to contact blockage or damage in the subterranean borehole,so that the damage or blockage is altered, removed, degraded, and/ordissolved, so that a permeability, a relative permeability, and/or anabsolute permeability of the subterranean formation is increased,causing an increase in the production rates and/or recovery ofhydrocarbons.

A method of removing filter cake from a subterranean borehole, themethod comprising: drilling a borehole with a drill-in fluid to form afilter cake; contacting the filter cake with a composition comprising(a) an encapsulated peroxygen; (b) a surfactant; and (c) anunencapsulated peroxygen; and allowing the composition to remaindownhole for a period of time sufficient to degrade the filter cake.

The method of paragraph [00106], wherein the peroxygen chemically breaksdown the filter cake via a direct oxidation pathway or via a freeradical pathway.

The method of paragraph [00106], further comprising removing thedegraded filter cake from the subterranean borehole.

The method of paragraph [00106], wherein the treatment generates acidicconditions.

The method of paragraph [00106], wherein the composition furthercomprises a variable density brine.

The method of paragraph [00106], wherein at least one component of thecomposition is mixed with fresh water, brine water, formation water withpotassium chloride or other salts added, or combinations thereof, priorto introduction into the subterranean borehole.

The method of paragraph [00106], wherein the encapsulated peroxygen isselected from the group consisting of encapsulated hydrogen peroxide, anencapsulated source of hydrogen peroxide, encapsulated sodiumpersulfate, encapsulated potassium persulfate, encapsulated ammoniumpersulfate, and combinations thereof.

The method of paragraph [00106], wherein the encapsulated peroxygen iscured acrylic resin encapsulated peroxygen.

The method of paragraph [00106], wherein the encapsulated peroxygen iscoated ammonium persulfate.

The method of paragraph [00106], wherein the encapsulated peroxygenprovides a controlled time release of the peroxygen.

The method of paragraph [00106], wherein the encapsulated peroxygen ispresent in an amount of at least 5 weight percent, based on the totalweight of the composition.

The method of paragraph [00106], wherein peroxygen from the encapsulatedperoxygen decomposes from a direct reduction reaction, a surfacecatalyzed reaction, and/or a free radical decomposition reaction.

The method of paragraph [00106], wherein the surfactant is nonionic.

The method of paragraph [00106], wherein the surfactant is selected fromthe group consisting of an ethoxylated plant oil based surfactant, afatty alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid amideethoxylate, a fatty acid ester, a fatty acid methyl ester ethoxylate, analkyl polyglucoside, a polyalcohol ethoxylate, a sorbitan ester, a soyalkyltrimethyl ammonium chloride, an ethoxylated coco fatty acid, anethoxylated coco fatty ester, an ethoxylated cocoamide, an ethoxylatedcastor oil, and combinations thereof.

The method of paragraph [00106], wherein the surfactant comprises anonionic surfactant selected from the group consisting of a fattyalcohol ethoxylate, a fatty acid ethoxylate, a fatty acid ester, a fattyacid methyl ester ethoxylate, an alkyl polyglucoside, a polyalcoholethoxylate, a soy alkyltrimethyl ammonium chloride, a monococoate, andcombinations thereof.

The method of paragraph [00106], wherein the surfactant comprises anonionic surfactant selected from the group consisting of an ethoxylatedcoco fatty acid, an ethoxylated coco fatty ester, an ethoxylatedcocoamide, an ethoxylated castor oil, a monococoate, and combinationsthereof.

The method of paragraph [00121], wherein the ethoxylated coco fatty acidis a polyethylene glycol (PEG) coco fatty acid having a range of about 5to about 40 PEG groups, and a Hydrophile-Lipophile Balance (HLB) rangefrom about 10 to about 19; the ethoxylated castor oil is a polyethyleneglycol (PEG) castor oil having a range of about 2.5 to about 40 PEGgroups, and a Hydrophile-Lipophile Balance (HLB) range from about 2.1 toabout 16; the ethoxylated cocoamide is a polyethylene glycol (PEG)cocamide having a range of about 2 to about 20 PEG groups, and aHydrophile-Lipophile Balance (HLB) range from about 2 to about 19.

The method of paragraph [00106], wherein the surfactant comprises asorbitan ester selected from the group consisting of sorbitan monooleatehaving a Hydrophile-Lipophile Balance (HLB) range from about 2.8 toabout 8.8; sorbitan monolaurate having a Hydrophile-Lipophile Balance(HLB) range from about 4.6 to about 12.6; sorbitan monopalmitate havinga Hydrophile-Lipophile Balance (HLB) range from about 2.5 to about 10.5;and sorbitan monostearate having a Hydrophile-Lipophile Balance (HLB)range from about 2.7 to about 8.7.

The method of paragraph [00106], wherein the surfactant comprises anethoxylated sorbitan ester selected from the group consisting of apolyethylene glycol (PEG) sorbitan monooleate having a range of about 2to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB)range from about 10 to about 20; a polyethylene glycol (PEG) sorbitanmonolaurate having a range of about 2 to about 40 PEG groups, and havinga Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; apolyethylene glycol (PEG) sorbitan monopalmitate having a range of about2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance(HLB) range from about 10 to about 20; and a polyethylene glycol (PEG)sorbitan monostearate having a range of about 2 to about 40 PEG groups,and having a Hydrophile-Lipophile Balance (HLB) range from about 10 toabout 20.

The method of paragraph [00106], wherein the surfactant is present inthe composition, when the composition is introduced into the wellbore orsubterranean formation, in an amount from about 0.01 to about 50 percentby weight, based on the total weight of the composition.

The method of paragraph [00106], wherein the unencapsulated peroxygen isselected from the group consisting of unencapsulated hydrogen peroxide,an unencapsulated source of hydrogen peroxide, unencapsulated sodiumpersulfate, unencapsulated potassium persulfate, unencapsulated ammoniumpersulfate, and combinations thereof.

The method of paragraph [00106], further comprising a chelate, whereinthe chelate is selected from the group consisting of a mono-, di-, tri-or tetra-sodium ethylenediaminetetraacetic acid (EDTA), a mono-, di-,tri- or tetra-potassium ethylenediaminetetraacetic acid (EDTA), sodiumethylenediamine-N,N′-disuccinic acid (EDDS), and combinations thereof.

The method of paragraph [00106], further comprising a cosolvent, whereinthe cosolvent is selected from the group consisting of a terpene, methylsoyate, ethyl lactate, methyl lactate, ethyl acetate, and combinationsthereof.

The method of paragraph [00106], wherein the composition is applied tothe subterranean borehole as, or in combination with, a drilling fluid,treatment fluid, stimulation fluid, fracturing fluid, a fluid used in anenhanced oil recovery technique, or a combination thereof.

The method of paragraph [00106], further comprising: allowing thecomponents to contact blockage or damage in the subterranean borehole,so that the damage or blockage is altered, removed, degraded, and/ordissolved, so that a permeability, a relative permeability, and/or anabsolute permeability of the subterranean formation is increased,causing an increase in the production rates and/or recovery ofhydrocarbons.

A method of removing filter cake from a subterranean borehole, themethod comprising: drilling a borehole with a drill-in fluid to form afilter cake; contacting the filter cake with a composition comprising(a) an unencapsulated peroxygen; and (b) a surfactant; and allowing thecomposition to remain downhole at a temperature from about 180° F. toabout 250° F. and for a period of time sufficient to degrade the filtercake.

The method of paragraph [00131], wherein the peroxygen chemically breaksdown the filter cake via a direct oxidation pathway or via a freeradical pathway.

The method of paragraph [00131], further comprising removing thedegraded filter cake from the subterranean borehole.

The method of paragraph [00131], wherein the treatment generates acidicconditions.

The method of paragraph [00131], wherein the composition furthercomprises a variable density brine.

The method of paragraph [00131], wherein at least one component of thecomposition is mixed with fresh water, brine water, formation water withpotassium chloride or other salts added, or combinations thereof, priorto introduction into the subterranean borehole.

The method of paragraph [00131], wherein the unencapsulated peroxygen isselected from the group consisting of unencapsulated hydrogen peroxide,an unencapsulated source of hydrogen peroxide, unencapsulated sodiumpersulfate, unencapsulated potassium persulfate, unencapsulated ammoniumpersulfate, and combinations thereof.

The method of paragraph [00131], wherein peroxygen from theunencapsulated peroxygen decomposes from a direct reduction reaction, asurface catalyzed reaction, and/or a free radical decompositionreaction.

The method of paragraph [00131], wherein the surfactant is nonionic.

The method of paragraph [00131], wherein the surfactant is selected fromthe group consisting of an ethoxylated plant oil based surfactant, afatty alcohol ethoxylate, a fatty acid ethoxylate, a fatty acid amideethoxylate, a fatty acid ester, a fatty acid methyl ester ethoxylate, analkyl polyglucoside, a polyalcohol ethoxylate, a sorbitan ester, a soyalkyltrimethyl ammonium chloride, an ethoxylated coco fatty acid, anethoxylated coco fatty ester, an ethoxylated cocoamide, an ethoxylatedcastor oil, and combinations thereof.

The method of paragraph [00131], wherein the surfactant comprises anonionic surfactant selected from the group consisting of a fattyalcohol ethoxylate, a fatty acid ethoxylate, a fatty acid ester, a fattyacid methyl ester ethoxylate, an alkyl polyglucoside, a polyalcoholethoxylate, a soy alkyltrimethyl ammonium chloride, a monococoate, andcombinations thereof.

The method of paragraph [00131], wherein the surfactant comprises anonionic surfactant selected from the group consisting of an ethoxylatedcoco fatty acid, an ethoxylated coco fatty ester, an ethoxylatedcocoamide, an ethoxylated castor oil, a monococoate, and combinationsthereof.

The method of paragraph [00142], wherein the ethoxylated coco fatty acidis a polyethylene glycol (PEG) coco fatty acid having a range of about 5to about 40 PEG groups, and a Hydrophile-Lipophile Balance (HLB) rangefrom about 10 to about 19; the ethoxylated castor oil is a polyethyleneglycol (PEG) castor oil having a range of about 2.5 to about 40 PEGgroups, and a Hydrophile-Lipophile Balance (HLB) range from about 2.1 toabout 16; the ethoxylated cocoamide is a polyethylene glycol (PEG)cocamide having a range of about 2 to about 20 PEG groups, and aHydrophile-Lipophile Balance (HLB) range from about 2 to about 19.

The method of paragraph [00131], wherein the surfactant comprises asorbitan ester selected from the group consisting of sorbitan monooleatehaving a Hydrophile-Lipophile Balance (HLB) range from about 2.8 toabout 8.8; sorbitan monolaurate having a Hydrophile-Lipophile Balance(HLB) range from about 4.6 to about 12.6; sorbitan monopalmitate havinga Hydrophile-Lipophile Balance (HLB) range from about 2.5 to about 10.5;and sorbitan monostearate having a Hydrophile-Lipophile Balance (HLB)range from about 2.7 to about 8.7.

The method of paragraph [00131], wherein the surfactant comprises anethoxylated sorbitan ester selected from the group consisting of apolyethylene glycol (PEG) sorbitan monooleate having a range of about 2to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB)range from about 10 to about 20; a polyethylene glycol (PEG) sorbitanmonolaurate having a range of about 2 to about 40 PEG groups, and havinga Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; apolyethylene glycol (PEG) sorbitan monopalmitate having a range of about2 to about 40 PEG groups, and having a Hydrophile-Lipophile Balance(HLB) range from about 10 to about 20; and a polyethylene glycol (PEG)sorbitan monostearate having a range of about 2 to about 40 PEG groups,and having a Hydrophile-Lipophile Balance (HLB) range from about 10 toabout 20.

The method of paragraph [00131], wherein the surfactant is present inthe composition, when the composition is introduced into the wellbore orsubterranean formation, in an amount from about 0.01 to about 50 percentby weight, based on the total weight of the composition.

The method of paragraph [00131], further comprising a chelate, whereinthe chelate is selected from the group consisting of a mono-, di-, tri-or tetra-sodium ethylenediaminetetraacetic acid (EDTA), a mono-, di-,tri- or tetra-potassium ethylenediaminetetraacetic acid (EDTA), sodiumethylenediamine-N,N′-disuccinic acid (EDDS), and combinations thereof.

The method of paragraph [00131], further comprising a cosolvent, whereinthe cosolvent is selected from the group consisting of a terpene, methylsoyate, ethyl lactate, methyl lactate, ethyl acetate, and combinationsthereof.

The method of paragraph [00131], wherein the composition is applied tothe subterranean borehole as, or in combination with, a drilling fluid,treatment fluid, stimulation fluid, fracturing fluid, a fluid used in anenhanced oil recovery technique, or a combination thereof.

The method of paragraph [00131], further comprising: allowing thecomponents to contact blockage or damage in the subterranean borehole,so that the damage or blockage is altered, removed, degraded, and/ordissolved, so that a permeability, a relative permeability, and/or anabsolute permeability of the subterranean formation is increased,causing an increase in the production rates and/or recovery ofhydrocarbons.

A composition for removing filter cake from a subterranean borehole, thecomposition comprising: (a) an encapsulated peroxygen; and (b) asurfactant.

A composition for removing filter cake from a subterranean borehole, thecomposition comprising: (a) an encapsulated peroxygen; (b) a surfactant;and (c) an unencapsulated peroxygen.

A one-step method for degrading filter cake, the method comprising:contacting the filter cake with a composition comprising (a) anencapsulated peroxygen; (b) a surfactant; and optionally (c) anunencapsulated peroxygen; and allowing the composition to remain incontact with the filter cake for a period of time sufficient to degradethe filter cake; wherein the method generates acidic conditions.

As used herein, “encapsulated” or “encapsulating” refers to the one ormore peroxygen compounds being covered by an encapsulating material ofthis disclosure. For example, the encapsulating material can form alayer or shell around the peroxygen compound, and/or encapsulate theperoxygen compound.

The terms “comprises” or “comprising” are interpreted as specifying thepresence of the stated features, integers, steps or components, but notprecluding the presence of one or more other features, integers, stepsor components or groups thereof.

It should be understood that various alternatives, combinations andmodifications of the present disclosure could be devised by thoseskilled in the art. For example, steps associated with the processesdescribed herein can be performed in any order, unless otherwisespecified or dictated by the steps themselves. The present disclosure isintended to embrace all such alternatives, modifications and variancesthat fall within the scope of the appended claims.

The following examples are provided to offer additional description ofthe compositions and methods disclosed and claimed in this patent. Theseare exemplary only, and are not intended to limit the disclosure in anyaspect. All proportions and percentages set out herein are by weightunless the contrary is stated.

EXAMPLE 1

Optimized oil-based drilling mud was prepared. The mud ingredients andamounts thereof are set forth in FIG. 1. A filter cake was formed usinga multi-mixer and a high temperature high pressure (HTHP) filtrationpress. A treatment solution was prepared in a KCl brine solution. Thefilter cake was soaked over 4 hours, 8 hours, and 20 hours. Filtratesolution was analyzed for ion concentrations. By measuring thefiltration rate before and after each test, the permeability ratio(k_(f)/k_(i)) was determined. The final permeability is designatedk_(f). The initial permeability is designated k_(i). The properties of acore sample are given in FIG. 2.

EXAMPLE 2

A blend composition containing a surfactant (i.e., ethoxylated cocofatty acid) and a coated persulfate (i.e., acrylic resin coated ammoniumpersulfate) was prepared. The blend was used in breaking of a filtercake formed in Example 1 and creation of acidic conditions. Theconditions used in breaking of the filter cake are given in FIG. 3. Thefilter cake removal results are given in FIG. 4. Photographs of thefilter cake removal results are also given in FIG. 4. A filtrateanalysis for Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe^(2+/3+) and Al³⁺ is given in FIG.5. Filter cake was successfully treated at 140° F. in 5 wt % KCl brine.The permeability ratio (k_(f)/k_(i)) was determined to be 1.125,indicating improved permeability.

EXAMPLE 3

A blend composition containing a surfactant (i.e., ethoxylated cocofatty acid) and a coated persulfate (i.e., acrylic resin coated ammoniumpersulfate) was prepared. The blend was used in breaking of a filtercake formed in Example 1 and creation of acidic conditions. Theconditions used in breaking of the filter cake are given in FIG. 6. Thefilter cake removal results are given in FIG. 7. Photographs of thefilter cake removal results are also given in FIG. 7. A filtrateanalysis for Na⁺, Ca⁺ and Fe^(2+/3+) is given in FIG. 8. Filter cake wassuccessfully treated at 190° F. within 4 hours, where 95% of the filtercake was removed. The permeability ratio (k_(f)/k_(i)) was determined tobe 2.1, indicating improved permeability.

EXAMPLE 4

A blend composition containing a surfactant (i.e., ethoxylated cocofatty acid) and a coated persulfate (i.e., acrylic resin coated ammoniumpersulfate) was prepared. The blend was used in breaking of a filtercake formed in Example 1 and creation of acidic conditions. Theconditions used in breaking of the filter cake are given in FIG. 9. Thefilter cake removal results are given in FIG. 10. Photographs of thefilter cake removal results are also given in FIG. 10. A filtrateanalysis for Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe^(2+/3+)and Al³⁺ is given in FIG.11. Filter cake was successfully treated at 190° F. within 8 hours,where 97% of the filter cake was removed. The permeability ratio(k_(f)/k_(i)) was determined to be 2.0, indicating improvedpermeability. As observed in FIG. 11, the treatment resulted in highlyacidic conditions, with a pH of below 1 after 4 hours.

EXAMPLE 5

A blend composition containing a surfactant (i.e., ethoxylated cocofatty acid) and a coated persulfate (i.e., acrylic resin coated ammoniumpersulfate) was prepared. The blend was used in breaking of a filtercake formed in Example 1 and creation of acidic conditions. Theconditions used in breaking of the filter cake are given in FIG. 12. Thefilter cake removal results are given in FIG. 13. Photographs of thefilter cake removal results are also given in FIG. 13. A filtrateanalysis for Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe^(2+/3+) and Al³⁺ is given in FIG.14. Filter cake was successfully treated at 250° F. within 8 hours,where 91% of the filter cake was removed. The permeability ratio(k_(f)/k_(i)) was determined to be 1.23, indicating improvedpermeability. As observed in FIG. 14, the treatment resulted in highlyacidic conditions, with a pH of below 1 after 4 hours.

EXAMPLE 6

Blend compositions containing a surfactant (i.e., ethoxylated coco fattyacid) and a coated persulfate (i.e., acrylic resin coated ammoniumpersulfate) were prepared. The blend compositions were used in breakingof a filter cake formed in Example 1 and creation of acidic conditions.The conditions used in breaking of the filter cake are given in FIG. 15,including various brine concentrations from 5% to 18% and at varioustemperatures from 140° F. to 250° F. Filter cake was successfullytreated under all tested conditions with removal efficiencies from 84%to 91% after 4 hours and up to 94% to 98% after 20 hours. Acidicconditions were created without an addition of acid, with a pH of below1 after 4 hours. A summary of all test results is given in FIG. 15.

What is claimed is:
 1. A composition for removing filter cake from asubterranean borehole, said composition comprising: (a) an encapsulatedpersulfate; and (b) a nonionic surfactant, wherein the encapsulatedpersulfate is present in an amount from about 0.01 to about 20 weightpercent, and the nonionic surfactant is present in an amount from about0.01 to about 50 weight percent, based on the total weight of saidcomposition, when said composition is introduced into the borehole; orsaid composition comprising: (a) an encapsulated persulfate; (b) anonionic surfactant; and (c) an unencapsulated persulfate, wherein theencapsulated persulfate is present in an amount from about 0.01 to about20 weight percent, the nonionic surfactant is present in an amount fromabout 0.01 to about 50 weight percent, and the unencapsulated persulfateis present in an amount from about 0.01 to about 20 weight percent,based on the total weight of said composition, when said composition isintroduced into the borehole.
 2. The composition of claim 1, furthercomprising a variable density brine.
 3. The composition of claim 1,wherein at least one component of the composition is mixed with freshwater, brine water, formation water with potassium chloride or othersalts added, or combinations thereof, prior to introduction into thesubterranean borehole.
 4. The composition of claim 1, wherein theencapsulated persulfate is selected from the group consisting ofencapsulated sodium persulfate, encapsulated potassium persulfate,encapsulated ammonium persulfate, and combinations thereof.
 5. Thecomposition of claim 1, wherein the encapsulated persulfate is curedacrylic resin encapsulated persulfate.
 6. The composition of claim 1,wherein the encapsulated persulfate is coated ammonium persulfate. 7.The composition of claim 1, wherein the encapsulated persulfate providesa controlled time release of the persulfate.
 8. The composition of claim1, wherein the persulfate from the encapsulated persulfate decomposesfrom a direct reduction reaction, a surface catalyzed reaction, and/or afree radical decomposition reaction.
 9. The composition of claim 1,wherein: the nonionic surfactant is selected from the group consistingof an ethoxylated plant oil based surfactant, a fatty alcoholethoxylate, a fatty acid ethoxylate, a fatty acid amide ethoxylate, afatty acid ester, a fatty acid methyl ester ethoxylate, an alkylpolyglucoside, a polyalcohol ethoxylate, a sorbitan ester, a soyalkyltrimethyl ammonium chloride, an ethoxylated coco fatty acid, anethoxylated coco fatty ester, an ethoxylated cocoamide, an ethoxylatedcastor oil, and combinations thereof; or the nonionic surfactant isselected from the group consisting of a fatty alcohol ethoxylate, afatty acid ethoxylate, a fatty acid ester, a fatty acid methyl esterethoxylate, an alkyl polyglucoside, a polyalcohol ethoxylate, a soyalkyltrimethyl ammonium chloride, a monococoate, and combinationsthereof; or the nonionic surfactant is selected from the groupconsisting of an ethoxylated coco fatty acid, an ethoxylated coco fattyester, an ethoxylated cocoamide, an ethoxylated castor oil, amonococoate, and combinations thereof; or the nonionic surfactantcomprises a sorbitan ester selected from the group consisting ofsorbitan monooleate having a Hydrophile-Lipophile Balance (HLB) rangefrom about 2.8 to about 8.8; sorbitan monolaurate having aHydrophile-Lipophile Balance (HLB) range from about 4.6 to about 12.6;sorbitan monopalmitate having a Hydrophile-Lipophile Balance (HLB) rangefrom about 2.5 to about 10.5; and sorbitan monostearate having aHydrophile-Lipophile Balance (HLB) range from about 2.7 to about 8.7; orthe nonionic surfactant comprises an ethoxylated sorbitan ester selectedfrom the group consisting of a polyethylene glycol (PEG) sorbitanmonooleate having a range of about 2 to about 40 PEG groups, and havinga Hydrophile-Lipophile Balance (HLB) range from about 10 to about 20; apolyethylene glycol (PEG) sorbitan monolaurate having a range of about 2to about 40 PEG groups, and having a Hydrophile-Lipophile Balance (HLB)range from about 10 to about 20; a polyethylene glycol (PEG) sorbitanmonopalmitate having a range of about 2 to about 40 PEG groups, andhaving a Hydrophile-Lipophile Balance (HLB) range from about 10 to about20; and a polyethylene glycol (PEG) sorbitan monostearate having a rangeof about 2 to about 40 PEG groups, and having a Hydrophile-LipophileBalance (HLB) range from about 10 to about
 20. 10. The composition ofclaim 9, wherein the ethoxylated coco fatty acid is a polyethyleneglycol (PEG) coco fatty acid having a range of about 5 to about 40 PEGgroups, and a Hydrophile-Lipophile Balance (HLB) range from about 10 toabout 19; the ethoxylated castor oil is a polyethylene glycol (PEG)castor oil having a range of about 2.5 to about 40 PEG groups, and aHydrophile-Lipophile Balance (HLB) range from about 2.1 to about 16; theethoxylated cocoamide is a polyethylene glycol (PEG) cocamide having arange of about 2 to about 20 PEG groups, and a Hydrophile-LipophileBalance (HLB) range from about 2 to about
 19. 11. The composition ofclaim 1, further comprising a chelate, wherein the chelate is selectedfrom the group consisting of a mono-, di-, tri- or tetra-sodiumethylenediaminetetraacetic acid (EDTA), a mono-, di-, tri- ortetra-potassium ethylenediaminetetraacetic acid (EDTA), sodiumethylenediamine-N,N′-disuccinic acid (EDDS), and combinations thereof.12. The composition of claim 1, further comprising a cosolvent, whereinthe cosolvent is selected from the group consisting of a terpene, methylsoyate, ethyl lactate, methyl lactate, ethyl acetate, and combinationsthereof
 13. The composition of claim 1, which is applied to thesubterranean borehole as, or in combination with, a drilling fluid,treatment fluid, stimulation fluid, fracturing fluid, a fluid used in anenhanced oil recovery technique, or a combination thereof